US10559826B2 - Multivalent metal ion battery having a cathode of recompressed graphite worms and manufacturing method - Google Patents
Multivalent metal ion battery having a cathode of recompressed graphite worms and manufacturing method Download PDFInfo
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- US10559826B2 US10559826B2 US15/463,555 US201715463555A US10559826B2 US 10559826 B2 US10559826 B2 US 10559826B2 US 201715463555 A US201715463555 A US 201715463555A US 10559826 B2 US10559826 B2 US 10559826B2
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- graphite
- cathode
- carbon
- multivalent metal
- ion battery
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- 239000010439 graphite Substances 0.000 title claims abstract description 229
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title description 3
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- 239000002184 metal Substances 0.000 claims abstract description 68
- 239000003792 electrolyte Substances 0.000 claims abstract description 60
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- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 10
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000005169 Debye-Scherrer Methods 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
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- 229910005813 NiMH Inorganic materials 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
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- KURZCZMGELAPSV-UHFFFAOYSA-N [Br].[I] Chemical compound [Br].[I] KURZCZMGELAPSV-UHFFFAOYSA-N 0.000 description 1
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- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229940003871 calcium ion Drugs 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
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- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
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- 239000012025 fluorinating agent Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
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- 230000002427 irreversible effect Effects 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 238000007734 materials engineering Methods 0.000 description 1
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- UTEAJUQTEFBYOE-UHFFFAOYSA-N methane;molecular bromine Chemical compound C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.C.BrBr UTEAJUQTEFBYOE-UHFFFAOYSA-N 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
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- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
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Images
Classifications
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Definitions
- the present invention relates generally to the field of rechargeable multivalent metal battery (e.g. zinc-, nickel-, magnesium-, or calcium-ion battery) and, more particularly, to a high-capacity cathode active layer of exfoliated graphite or carbon worms and a method of manufacturing the multivalent metal-ion battery.
- rechargeable multivalent metal battery e.g. zinc-, nickel-, magnesium-, or calcium-ion battery
- a high-capacity cathode active layer of exfoliated graphite or carbon worms e.g. zinc-, nickel-, magnesium-, or calcium-ion battery
- lithium-ion batteries Historically, today's most favorite rechargeable energy storage devices—lithium-ion batteries—was actually evolved from rechargeable “lithium metal batteries” that use lithium (Li) metal as the anode and a Li intercalation compound (e.g. MoS 2 ) as the cathode.
- Li metal is an ideal anode material due to its light weight (the lightest metal), high electronegativity ( ⁇ 3.04 V vs. the standard hydrogen electrode), and high theoretical capacity (3,860 mAh/g). Based on these outstanding properties, lithium metal batteries were proposed 40 years ago as an ideal system for high energy-density applications.
- cathode active materials have a relatively low lithium diffusion coefficient (typically D ⁇ 10 ⁇ 16 -10 ⁇ 11 cm 2 /sec). These factors have contributed to one major shortcoming of today's Li-ion batteries—a moderate energy density (typically 150-220 Wh/kg cell ) but extremely low power density (typically ⁇ 0.5 kW/kg).
- Supercapacitors are being considered for electric vehicle (EV), renewable energy storage, and modern grid applications.
- the relatively high volumetric capacitance density of a supercapacitor (10 to 100 times greater than those of electrolytic capacitors) derives from using porous electrodes to create a large surface area conducive to the formation of diffuse double layer charges.
- This electric double layer capacitance (EDLC) is created naturally at the solid-electrolyte interface when voltage is imposed. This implies that the specific capacitance of a supercapacitor is directly proportional to the specific surface area of the electrode material, e.g. activated carbon. This surface area must be accessible by the electrolyte and the resulting interfacial zones must be sufficiently large to accommodate the EDLC charges.
- This EDLC mechanism is based on surface ion adsorption.
- the required ions are pre-existing in a liquid electrolyte and do not come from the opposite electrode.
- the required ions to be deposited on the surface of a negative electrode (anode) active material e.g., activated carbon particles
- the required ions to be deposited on the surface of a cathode active material do not come from the anode side.
- a supercapacitor is re-charged, local positive ions are deposited close to a surface of a negative electrode with their matting negative ions staying close side by side (typically via local molecular or ionic polarization of charges).
- negative ions are deposited close to a surface of this positive electrode with the matting positive ions staying close side by side. Again, there is no exchange of ions between an anode active material and a cathode active material.
- the stored energy is further augmented by pseudo-capacitance effects due to some local electrochemical reactions (e.g., redox).
- redox some local electrochemical reactions
- the ions involved in a redox pair also pre-exist in the same electrode. Again, there is no exchange of ions between the anode and the cathode.
- EDL supercapacitor Since the formation of EDLC does not involve a chemical reaction or an exchange of ions between the two opposite electrodes, the charge or discharge process of an EDL supercapacitor can be very fast, typically in seconds, resulting in a very high power density (typically 3-10 kW/Kg). Compared with batteries, supercapacitors offer a higher power density, require no maintenance, offer a much higher cycle-life, require a very simple charging circuit, and are generally much safer. Physical, rather than chemical, energy storage is the key reason for their safe operation and extraordinarily high cycle-life.
- supercapacitors possess very low energy densities when compared to batteries (e.g., 5-8 Wh/kg for commercial supercapacitors vs. 10-30 Wh/Kg for the lead acid battery and 50-100 Wh/kg for the NiMH battery).
- Modern lithium-ion batteries possess a much higher energy density, typically in the range of 150-220 Wh/kg, based on the cell weight.
- alkaline Zn/MnO 2 nickel metal hydride (Ni-MH), lead-acid (Pb acid), and nickel-cadmium (Ni—Cd) batteries. Since their invention in 1860, alkaline Zn/MnO 2 batteries have become a highly popular primary (non-rechargeable) battery. It is now known that the Zn/MnO 2 pair can constitute a rechargeable battery if an acidic salt electrolyte, instead of basic (alkaline) salt electrolyte, is utilized. However, the cycle life of alkaline manganese dioxide rechargeable batteries has been limited to typically 20-30 cycles due to irreversibility associated with MnO 2 upon deep discharge and formation of electrochemically inactive phases.
- the invention provides a multivalent metal-ion battery comprising an anode, a cathode, and an electrolyte in ionic contact with the anode and the cathode to support reversible deposition and dissolution of a multivalent metal (selected from Ni, Zn, Be, Mg, Ca, Ba, La, Ti, Ta, Zr, Nb, Mn, V, Co, Fe, Cd, Cr, Ga, In, or a combination thereof) at the anode, wherein the anode contains the multivalent metal or its alloy as an anode active material and the cathode comprises a cathode active layer of exfoliated graphite or carbon material having inter-flake pores from 2 nm to 10 ⁇ m in pore size.
- the multivalent metal alloy preferably contains at least 80% by weight of the multivalent element in the alloy (more preferably at least 90% by weight). There is no restriction on the type of alloying elements that can be chosen.
- the exfoliated carbon or graphite material in the cathode active layer may be selected from a thermally exfoliated product of meso-phase pitch, meso-phase carbon, meso carbon micro-beads (MCMB), coke particles, expanded graphite flakes, artificial graphite particles, natural graphite particles, highly oriented pyrolytic graphite, soft carbon particles, hard carbon particles, multi-walled carbon nanotubes, carbon nano-fibers, carbon fibers, graphite nano-fibers, graphite fibers, carbonized polymer fibers, or a combination thereof.
- These carbon/graphite materials can be subjected to an expansion treatment (e.g. intercalation, oxidation, and/or fluorination), followed by thermal exfoliation to obtain exfoliated graphite/carbon worms.
- the exfoliated graphite/carbon worms are preferably recompressed to form a cathode active layer of recompressed exfoliated graphite or carbon material that is oriented in such a manner that the layer has a graphite edge plane in direct contact with the electrolyte (to readily admit ions from the electrolyte and release ions into electrolyte) and facing or touching the separator (so that the ions permeating through the porous separator can readily enter the inter-flake spaces near the edge plane).
- the layer of recompressed exfoliated graphite or carbon material has a physical density from 0.5 to 1.8 g/cm 3 and has meso-scaled pores having a pore size from 2 nm to 50 nm. In some preferred embodiments, the layer of recompressed exfoliated graphite or carbon material has a physical density from 1.1 to 1.8 g/cm 3 and has pores having a pore size from 2 nm to 5 nm. In certain embodiments, the exfoliated graphite or carbon material has a specific surface area from 10 to 1,500 m 2 /g. The specific surface area of the recompressed worms is typically from 10 to 1,000 m 2 /g, but more typically and preferably from 20 to 300 m 2 /g.
- a select multivalent metal e.g. Ni, Zn, Be, Mg, Ca, Ba, La, Ti, Ta, Zr, Nb, Mn, V, Co, Fe, Cd, Ga, In, or Cr
- a discharge curve plateau at approximately 1.0 volt or higher (up to 3.7 volts).
- This plateau regime of a discharge voltage vs. time (or capacity) curve enables the battery cell to provide a useful constant voltage output.
- a voltage output significantly lower than 1 volt is generally considered undesirable.
- the specific capacity corresponding to this plateau regime is typically from approximately 100 mAh/g to above 600 mAh/g.
- This multivalent metal-ion battery can further comprise an anode current collector supporting the aluminum metal or aluminum metal alloy or further comprise a cathode current collector supporting the cathode active layer.
- the current collector can be a mat, paper, fabric, foil, or foam that is composed of conducting nano-filaments, such as graphene sheets, carbon nanotubes, carbon nano-fibers, carbon fibers, graphite nano-fibers, graphite fibers, carbonized polymer fibers, or a combination thereof, which form a 3D network of electron-conducting pathways.
- the high surface areas of such an anode current collector not only facilitate fast and uniform dissolution and deposition of metal ions, but also act to reduce the exchange current density and, thus, the tendency to form metal dendrites that otherwise could cause internal shorting.
- the carbon or graphite material such as meso-phase pitch, meso-phase carbon, meso carbon micro-beads (MCMB), coke particles, expanded graphite flakes, artificial graphite particles, natural graphite particles, highly oriented pyrolytic graphite, soft carbon particles, hard carbon particles, multi-walled carbon nanotubes, carbon nano-fibers, carbon fibers, graphite nano-fibers, graphite fibers, and carbonized polymer fibers, has an original inter-planar spacing d 002 from 0.27 nm to 0.42 nm prior to a chemical or physical expansion treatment and the inter-planar spacing d 002 . is increased to from 0.43 nm to 2.0 nm after the expansion treatment.
- the expansion treatment includes an expansion treatment includes an oxidation, fluorination, bromination, chlorination, nitrogenation, intercalation, combined oxidation-intercalation, combined fluorination-intercalation, combined bromination-intercalation, combined chlorination-intercalation, or combined nitrogenation-intercalation of the graphite or carbon material.
- This expansion treatment is followed by thermal exfoliation and recompression. Due to the expansion treatments, the carbon or graphite material can contain a non-carbon element selected from oxygen, fluorine, chlorine, bromine, iodine, nitrogen, hydrogen, or boron.
- Unconstrained thermal exfoliation typically results in exfoliated graphite/carbon worms that have inter-flake pores having an average size from 20 nm to 50 ⁇ m (more typically from 100 nm to 10 ⁇ m).
- the exfoliated graphite/carbon worms are then compressed to produce a layer or block of recompressed exfoliated carbon or graphite material that is oriented in such a manner that the layer has a graphite edge plane in direct contact with the electrolyte and facing or contacting the separator.
- the recompressed exfoliated carbon or graphite material typically has a physical density from 0.5 to 1.8 g/cm 3 and has meso-scaled pores having a pore size from 2 nm to 50 nm.
- the electrolyte may be selected from an aqueous electrolyte, organic electrolyte, polymer electrolyte, molten salt electrolyte, ionic liquid electrolyte, or a combination thereof.
- the electrolyte may contain NiSO 4 , ZnSO 4 , MgSO 4 , CaSO 4 , BaSO 4 , FeSO 4 , MnSO 4 , CoSO 4 , VSO 4 , TaSO 4 , CrSO 4 , CdSO 4 , GaSO 4 , Zr(SO 4 ) 2 , Nb 2 (SO 4 ) 3 , La 2 (SO 4 ) 3 , BeCl 2 , BaCl 2 , MgCl 2 , AlCl 3 , Be(ClO 4 ) 2 , Ca(ClO 4 ) 2 , Mg(ClO 4 ) 2 , Mg(BF 4 ) 2 , Ca(BF 4 ) 2 , Be(BF
- the electrolyte comprises at least a metal ion salt selected from a transition metal sulphate, transition metal phosphate, transition metal nitrate, transition metal acetate, transition metal carboxylate, transition metal chloride, transition metal bromide, transition metal perchlorate, transition metal hexafluorophosphate, transition metal borofluoride, transition metal hexafluoroarsenide, or a combination thereof.
- a metal ion salt selected from a transition metal sulphate, transition metal phosphate, transition metal nitrate, transition metal acetate, transition metal carboxylate, transition metal chloride, transition metal bromide, transition metal perchlorate, transition metal hexafluorophosphate, transition metal borofluoride, transition metal hexafluoroarsenide, or a combination thereof.
- the electrolyte comprises at least a metal ion salt selected from a metal sulphate, phosphate, nitrate, acetate, carboxylate, chloride, bromide, or perchlorate of zinc, aluminum, titanium, magnesium, beryllium, calcium, manganese, cobalt, nickel, iron, vanadium, tantalum, gallium, chromium, cadmium, niobium, zirconium, lanthanum, or a combination thereof.
- a metal ion salt selected from a metal sulphate, phosphate, nitrate, acetate, carboxylate, chloride, bromide, or perchlorate of zinc, aluminum, titanium, magnesium, beryllium, calcium, manganese, cobalt, nickel, iron, vanadium, tantalum, gallium, chromium, cadmium, niobium, zirconium, lanthanum, or a combination thereof.
- the electrolyte comprises an organic solvent selected from ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), methyl butyrate (MB), ethyl propionate, methyl propionate, propylene carbonate (PC), ⁇ -butyrolactone ( ⁇ -BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), tetrahydrofuran (THF), toluene, xylene, methyl acetate (MA), or a combination thereof.
- organic solvent selected from ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), methyl butyrate (MB), ethyl propionate, methyl propionate, propylene carbonate (PC), ⁇ -butyrolactone ( ⁇ -BL),
- the layer of exfoliated carbon or graphite material also operates as a cathode current collector to collect electrons during a discharge of the battery and wherein the battery contains no separate or additional cathode current collector.
- the cathode active layer of exfoliated graphite/carbon may further comprise a binder material (preferably an electrically conductive binder material), which bonds exfoliated graphite flakes together to form a cathode electrode layer.
- a binder material preferably an electrically conductive binder material
- the electrically conductive binder material may be selected from coal tar pitch, petroleum pitch, meso-phase pitch, a conducting polymer, a polymeric carbon, or a derivative thereof.
- Non-conducting materials e.g. PVDF, PTFE, SBR, etc. may also be used.
- the invented secondary battery has an average discharge voltage typically no less than 1 volt (more typically and preferably >1.5 volts) and a cathode specific capacity greater than 200 mAh/g (preferably and more typically >300 mAh/g, more preferably >400 mAh/g, and most preferably >500 mAh/g) based on a total cathode active layer weight.
- Some cells deliver a specific capacity >600 mAh/g.
- the secondary battery has an average discharge voltage no less than 2.0 volts (preferably >2.5 volts, more preferably >3.0 volts, and most preferably >3.5 volts) and a cathode specific capacity greater than 100 mAh/g based on a total cathode active layer weight (preferably and more typically >200 mAh/g, more preferably >300 mAh/g, and most preferably >500 mAh/g).
- the present invention also provides a method of manufacturing a multivalent metal-ion battery.
- the method comprises: (a) providing an anode containing a multivalent metal (selected from Ni, Zn, Be, Mg, Ca, Ba, La, Ti, Ta, Zr, Nb, Mn, V, Co, Fe, Cd, Cr, Ga, In, or a combination thereof) or its alloy; (b) providing a cathode comprising a layer of recompressed exfoliated carbon or graphite material (recompressed graphite/carbon worms or recompressed expanded graphite flakes, not graphene sheets); and (c) providing an electrolyte capable of supporting reversible deposition and dissolution of the multivalent metal at the anode and reversible adsorption/desorption and/or intercalation/de-intercalation of ions at the cathode; wherein the layer of recompressed exfoliated carbon or graphite material is oriented in such a manner that the layer has
- this graphite edge plane is substantially parallel to the porous separator and, thus, can readily admit and accommodate ions that migrate through the separator.
- the electrolyte contains an aqueous electrolyte, an organic electrolyte, a molten salt electrolyte, or an ionic liquid.
- the method can further include providing a porous network of electrically conductive nano-filaments to support the multivalent metal or its alloy at the anode.
- the step of providing a cathode preferably contains subjecting a carbon or graphite material to an expansion treatment selected from an oxidation, fluorination, bromination, chlorination, nitrogenation, intercalation, combined oxidation-intercalation, combined fluorination-intercalation, combined bromination-intercalation, combined chlorination-intercalation, or combined nitrogenation-intercalation, followed by thermal exfoliation at a temperature from 100° C. to 2,500° C.
- an expansion treatment selected from an oxidation, fluorination, bromination, chlorination, nitrogenation, intercalation, combined oxidation-intercalation, combined fluorination-intercalation, combined bromination-intercalation, combined chlorination-intercalation, or combined nitrogenation-intercalation, followed by thermal exfoliation at a temperature from 100° C. to 2,500° C.
- the procedure of providing the cathode includes compressing exfoliated graphite or carbon using a wet compression or dry compression to align constituent graphite flakes of the exfoliated graphite or carbon.
- the procedure can produce a layer or block of graphitic structure having a flake edge plane being parallel to the separator, enabling direct entry of ions from separator pores into inter-flake spaces with minimal resistance.
- the procedure of providing the cathode includes compressing exfoliated graphite or carbon using a wet compression to align constituent graphite flakes of the exfoliated graphite or carbon, wherein wet compression includes compressing or pressing a suspension of exfoliated graphite or carbon dispersed in a liquid electrolyte intended for use in a multivalent metal-ion cell.
- wet compression includes compressing or pressing a suspension of exfoliated graphite or carbon dispersed in a liquid electrolyte intended for use in a multivalent metal-ion cell.
- Any of the aforementioned electrolytes can be utilized in this suspension.
- the electrolyte later becomes part of the electrolyte of the intended multivalent metal-ion battery.
- FIG. 1(A) Schematic drawing illustrating the processes for producing intercalated and/or oxidized graphite, subsequently exfoliated graphite worms, and conventional paper, mat, film, and membrane of simply aggregated graphite or graphene flakes/platelets;
- FIG. 1(B) An SEM image of exfoliated carbon (exfoliated carbon worms);
- FIG. 1(C) An SEM image of graphite worms
- FIG. 1(D) Schematic drawing illustrating the approaches of producing thermally exfoliated graphite structures.
- FIG. 1(E) A continuous process of producing recompressed exfoliated graphite, including feeding dry exfoliated graphite worms into the gap between a pair of two counter-rotating rollers or the gaps between several pairs of rollers.
- FIG. 1(F) A schematic drawing to illustrate an example of a compressing and consolidating operation (using a mold cavity cell 302 equipped with a piston or ram 308 ) for forming a layer of highly compacted and oriented graphite flakes.
- FIG. 1(G) Schematic drawing to illustrate another example of a compressing and consolidating operation (using a mold cavity cell equipped with a piston or ram) for forming a layer of highly compacted and oriented graphite flakes.
- FIG. 2(A) Schematic of a multivalent metal secondary battery, wherein the anode layer is a thin multivalent metal coating or foil and the cathode active material layer contains a layer of thermally exfoliated graphite/carbon; and
- FIG. 2(B) Schematic of a multivalent metal secondary battery cell, wherein the anode layer is a thin multivalent metal coating or foil and the cathode active material layer is composed of thermally exfoliated graphite/carbon, an optional conductive additive (not shown) and an optional binder (not shown).
- FIG. 3(A) The discharge curves of three Zn foil anode-based Zn-ion cells; first one containing a cathode layer of original graphite particles, second one containing a cathode layer of thermally exfoliated graphite (with only light recompression; pore size from 20 nm to 3 ⁇ m), and third one containing a cathode layer of thermally exfoliated graphite (with heavy recompression; pore size range from approximately 2 nm to 20 nm; having an edge plane being parallel to the separator and in ion-contact with the separator).
- FIG. 3(B) The discharge curves of two Ca-ion cells; one containing a cathode layer of thermally exfoliated graphite (with heavy recompression) having an edge plane being parallel to the separator and in ionic contact with the separator); the other having a graphite flake surface plane being parallel to the separator and in contact with the separator.
- the cell containing a cathode of original artificial graphite particles exhibits a very short discharge curve ( ⁇ 30 mAh/g); not shown in the chart.
- FIG. 4 The discharge curves of two Ni mesh anode-based cells; one containing a cathode layer of original MCMB particles and the other a cathode layer of thermally exfoliated MCMB worms.
- FIG. 5 The specific capacity of a Zn-MCMB cell (containing a cathode layer of recompressed exfoliated MCMB) and a V-CNF (containing a cathode of vapor grown carbon nanofibers exfoliated and recompressed), both plotted as a function of the number of charge/discharge cycles.
- FIG. 6 The specific capacity of a Mg-ion cell containing a cathode layer of heavily recompressed exfoliated MCMBs and favorably oriented; and the specific capacity of a Mg-ion cell containing a cathode of lightly recompressed exfoliated MCMBs, both plotted as a function of the number of charge/discharge cycles.
- the electrolyte used was 1 M of MgCl 2 :AlCl 3 (2:1) in monoglyme.
- bulk natural graphite is a 3-D graphitic material with each graphite particle being composed of multiple grains (a grain being a graphite single crystal or crystallite) with grain boundaries (amorphous or defect zones) demarcating neighboring graphite single crystals.
- Each grain is composed of multiple graphene planes that are oriented parallel to one another.
- a graphene plane or hexagonal carbon atom plane in a graphite crystallite is composed of carbon atoms occupying a two-dimensional, hexagonal lattice.
- the graphene planes are stacked and bonded via van der Waal forces in the crystallographic c-direction (perpendicular to the graphene plane or basal plane).
- the inter-graphene plane spacing in a natural graphite material is approximately 0.3354 nm.
- Artificial graphite materials also contain constituent graphene planes, but they have an inter-graphene planar spacing, d 002 , typically from 0.32 nm to 0.36 nm (more typically from 0.3339 to 0.3465 nm), as measured by X-ray diffraction.
- Many carbon or quasi-graphite materials also contain graphite crystals (also referred to as graphite crystallites, domains, or crystal grains) that are each composed of stacked graphene planes. These include meso-carbon mocro-beads (MCMBs), meso-phase carbon, soft carbon, hard carbon, coke (e.g.
- MW-CNT multi-walled carbon nanotubes
- the “soft carbon” refers to a carbon material containing graphite domains wherein the orientation of the hexagonal carbon planes (or graphene planes) in one domain and the orientation in neighboring graphite domains are not too mis-matched from each other so that these domains can be readily merged together when heated to a temperature above 2,000° C. (more typically above 2,500° C.). Such a heat treatment is commonly referred to as graphitization.
- the soft carbon can be defined as a carbonaceous material that can be graphitized.
- a “hard carbon” can be defined as a carbonaceous material that contain highly mis-oriented graphite domains that cannot be thermally merged together to obtain larger domains; i.e.
- the hard carbon cannot be graphitized. Both hard carbon and soft carbon contain graphite domains that can be intercalated and thermally exfoliated. The exfoliated carbon then can be recompressed to produce a cathode layer having constituent graphite flakes being aligned.
- the spacing between constituent graphene planes of a graphite crystallite in a natural graphite, artificial graphite, and other graphitic carbon materials in the above list can be expanded (i.e. the d 002 spacing being increased from the original range of 0.27-0.42 nm to the range of 0.42-2.0 nm) using several expansion treatment approaches, including oxidation, fluorination, chlorination, bromination, iodization, nitrogenation, intercalation, combined oxidation-intercalation, combined fluorination-intercalation, combined chlorination-intercalation, combined bromination-intercalation, combined iodization-intercalation, or combined nitrogenation-intercalation of the graphite or carbon material.
- expansion treatment approaches including oxidation, fluorination, chlorination, bromination, iodization, nitrogenation, intercalation, combined oxidation-intercalation, combined fluorination-intercalation, combined chlorination-intercalation, combined bromination-intercalation,
- graphite can be treated so that the spacing between the graphene planes can be increased to provide a marked expansion in the c-axis direction.
- the inter-planar spacing (also referred to as inter-graphene spacing) of graphite crystallites can be increased (expanded) via several approaches, including oxidation, fluorination, and/or intercalation of graphite. This is schematically illustrated in FIG. 1(D) .
- an intercalant, oxygen-containing group, or fluorine-containing group serves to increase the spacing between two graphene planes in a graphite crystallite and weaken the van der Waals forces between graphene planes, enabling easier thermal exfoliation.
- the inter-planar spaces between certain graphene planes may be significantly increased (actually, exfoliated) if the graphite/carbon material having expanded d spacing is exposed to a thermal shock (e.g. by rapidly placing this carbon material in a furnace pre-set at a temperature of typically 800-2,500° C.) without constraint (i.e. being allowed to freely increase volume).
- a thermal shock e.g. by rapidly placing this carbon material in a furnace pre-set at a temperature of typically 800-2,500° C.
- constraint i.e. being allowed to freely increase volume
- the thermally exfoliated graphite/carbon material appears like worms, wherein each graphite worm is composed of many graphite flakes remaining interconnected (please see FIG. 1(C) ).
- these graphite flakes have inter-flake pores typically in the pore size range of 20 nm to 10 ⁇ m.
- graphite materials having an expanded inter-planar spacing are obtained by intercalating natural graphite particles with a strong acid and/or an oxidizing agent to obtain a graphite intercalation compound (GIC) or graphite oxide (GO), as illustrated in FIG. 1(A) .
- GIC graphite intercalation compound
- GO graphite oxide
- the presence of chemical species or functional groups in the interstitial spaces between graphene planes serves to increase the inter-graphene spacing, d 002 , as determined by X-ray diffraction, thereby significantly reducing the van der Waals forces that otherwise hold graphene planes together along the c-axis direction.
- the GIC or GO is most often produced by immersing natural graphite powder ( 100 in FIG.
- GIC graphite oxide
- Expandable graphite is essentially a mass of dried GIC or dried graphite oxide particles.
- the inter-graphene spacing, d 002 , in the dried GIC or graphite oxide particles is typically in the range of 0.42-2.0 nm, more typically in the range of 0.5-1.2 nm. It may be noted than the “expandable graphite” is not “expanded graphite” (to be further explained later).
- Graphite oxide can have an oxygen content of 2%-50% by weight, more typically 20%-40% by weight.
- Graphite worms are each a collection of exfoliated, but largely un-separated graphite flakes that remain interconnected ( FIGS. 1(B) and 1(C) ).
- exfoliated graphite individual graphite flakes (each containing 1 to several hundred of graphene planes stacked together) are highly spaced from one another, having a spacing of typically 2.0 nm-10 ⁇ m. However, they remain physically interconnected, forming an accordion or worm-like structure.
- Exfoliated graphite worms can be mechanically compressed to obtain “recompressed exfoliated graphite” for the purpose of densifying the mass of exfoliated graphite worms, reducing inter-flake pore sizes or spaces, and aligning the orientation of the constituent flakes.
- the graphite worms are extremely heavily compressed to form flexible graphite sheets or foils 106 that typically have a thickness in the range of 0.1 mm-0.5 mm.
- exfoliated graphite worms are compressed to the extent that the constituent graphite flakes are more or less parallel to one another and the edges of these flakes define an edge plane of the resulting block or layer of re-compressed graphite worms.
- Primary surfaces of some of the graphite flakes can constitute a flake surface plane (as opposed to the edge plane).
- the “expandable graphite” can be thermally exfoliated to obtain “graphite worms,” which, in turn, can be subjected to mechanical shearing to break up the otherwise interconnected graphite flakes to obtain “expanded graphite” flakes.
- Expanded graphite flakes typically have the same or similar inter-planar spacing (typically 0.335-0.36 nm) of their original graphite. Expanded graphite is not graphene either.
- Expanded graphite flakes have a thickness typically greater than 100 nm; in contrast, graphene sheets typically have a thickness smaller than 100 nm, more typically less than 10 nm, and most typically less than 3 nm (single layer graphene is 0.34 nm thick). In the present invention, expanded graphite flakes may also be compressed to form a layer of recompressed graphite having the desired orientation.
- the exfoliated graphite or graphite worms may be subjected to high-intensity mechanical shearing (e.g. using an ultrasonicator, high-shear mixer, high-intensity air jet mill, or high-energy ball mill) to form separated single-layer and multi-layer graphene sheets (collectively called NGPs, 112 ), as disclosed in our U.S. application Ser. No. 10/858,814.
- Single-layer graphene can be as thin as 0.34 nm, while multi-layer graphene can have a thickness up to 100 nm, but more typically less than 3 nm (commonly referred to as few-layer graphene).
- Multiple graphene sheets or platelets may be made into a sheet of NGP paper ( 114 ) using a paper-making process.
- the “expandable graphite” or graphite with expanded inter-planar spacing may also be obtained by forming graphite fluoride (GF), instead of GO.
- GF graphite fluoride
- Interaction of F 2 with graphite in a fluorine gas at high temperature leads to covalent graphite fluorides, from (CF) n to (C 2 F) n , while at low temperatures graphite intercalation compounds (GIC) C x F (2 ⁇ x ⁇ 24) form.
- GIC graphite intercalation compounds
- carbon atoms are sp3-hybridized and thus the fluorocarbon layers are corrugated consisting of trans-linked cyclohexane chairs.
- C x F lightly fluorinated graphite, C x F (2 ⁇ x ⁇ 24), obtained from electrochemical fluorination, typically has an inter-graphene spacing (d 002 ) less than 0.37 nm, more typically ⁇ 0.35 nm. Only when x in C x F is less than 2 (i.e. 0.5 ⁇ x ⁇ 2) can one observe a d 002 spacing greater than 0.5 nm (in fluorinated graphite produced by a gaseous phase fluorination or chemical fluorination procedure). When x in C x F is less than 1.33 (i.e. 0.5 ⁇ x ⁇ 1.33) one can observe a d 002 spacing greater than 0.6 nm.
- d 002 inter-graphene spacing
- This heavily fluorinated graphite is obtained by fluorination at a high temperature (>>200° C.) for a sufficiently long time, preferably under a pressure >1 atm, and more preferably >3 atm.
- electrochemical fluorination of graphite leads to a product having a d spacing less than 0.4 nm even though the product C x F has an x value from 1 to 2. It is possible that F atoms electrochemically introduced into graphite tend to reside in defects, such as grain boundaries, instead of between graphene planes and, consequently, do not act to expand the inter-graphene planar spacing.
- the nitrogenation of graphite can be conducted by exposing a graphite oxide material to ammonia at high temperatures (200-400° C.). Nitrogenation may also be conducted at lower temperatures by a hydrothermal method; e.g. by sealing GO and ammonia in an autoclave and then increased the temperature to 150-250° C.
- Compression or re-compression of exfoliated graphite worms or expanded graphite flakes into a layer or block of recompressed exfoliated graphite having a preferred graphite flake orientation can be accomplished by using several procedures, which can be classified into two broad categories: dry pressing/rolling or wet pressing/rolling.
- the dry process entails mechanically pressing graphite worms or expanded graphite flakes in one direction (uniaxial compression) without the presence of a liquid medium.
- the process includes feeding dry exfoliated graphite worms 30 into the gap between two counter-rotating rollers (e.g.
- a layer of oriented, recompressed exfoliated graphite structure may be cut and slit to produce a desired number of pieces of the oriented, recompressed exfoliated graphite structure. Assuming that each piece is a cube or tetragon, each cube will then have 4 graphite flake edge planes and 2 flake surface planes as illustrated in the bottom right portion of FIG. 1(D) . When such a piece is implemented as a cathode layer, the layer can be positioned and aligned in such a manner that one of the flake edge planes is substantially parallel to the anode layer or the porous separator layer. This flake edge plane typically is very close to or actually in direct contact with the separator layer. Such an orientation is found to be conducive to entry and exiting of ions into/from the electrode, leading to significantly improved high-rate capability and high power density.
- the same procedures can be used to produce a wet layer of recompressed exfoliated graphite provided the starting material contains graphite worms dispersed in a liquid medium.
- This liquid medium may be simply water or solvent, which must be removed upon completion of the roll-pressing procedure.
- the liquid medium may be or may contain a resin binder that helps to bond together exfoliated graphite worms or flakes, although a resin binder is not required or desired.
- some amount of the liquid electrolyte may be mixed with the exfoliated graphite worms or expanded graphite flakes prior to being compressed or roll-pressed.
- the present invention also provides a wet process for producing an electrolyte-impregnated recompressed graphite structure for use as a multivalent metal-ion battery cathode layer.
- the wet process comprises: (a) preparing a dispersion or slurry having exfoliated graphite worms or expanded graphite flakes dispersed in a liquid or gel electrolyte; and (b) subjecting the suspension to a forced assembly procedure, forcing the exfoliated graphite worms or expanded graphite flakes to assemble into the electrolyte-impregnated re-compressed graphite structure, wherein electrolyte resides in the inter-flake spaces in recompressed exfoliated graphite.
- the graphite flakes of the exfoliated graphite or the expanded graphite flakes are substantially aligned along a desired direction.
- the recompressed graphite structure has a physical density from 0.5 to 1.7 g/cm 3 (more typically 0.7-1.3 g/cm 3 ) and a specific surface area from 20 to 1,500 m 2 /g, when measured in a dried state of the recompressed graphite structure with the electrolyte removed.
- the forced assembly procedure includes introducing an exfoliated graphite suspension, having an initial volume V 1 , in a mold cavity cell and driving a piston into the mold cavity cell to reduce the suspension volume to a smaller value V 2 , allowing excess electrolyte to flow out of the cavity cell (e.g. through holes of the mold cavity cell or of the piston) and aligning the multiple graphite flakes along a direction at an angle from approximately 45° to 90° relative to the movement direction of the piston. It may be noted that the electrolyte used in this suspension becomes portion of the electrolyte for the intended multivalent metal-ion cell.
- FIG. 1(F) provides a schematic drawing to illustrate an example of a compressing and consolidating operation (using a mold cavity cell 302 equipped with a piston or ram 308 ) for forming a layer of highly compacted and oriented graphite flakes 314 .
- Contained in the chamber (mold cavity cell 302 ) is a suspension (or slurry) that is composed of graphite flakes 304 randomly dispersed in a liquid or gel electrolyte 306 .
- the piston 308 is driven downward, the volume of the suspension is decreased by forcing excess liquid electrolyte to flow through minute channels 312 on a mold wall or through small channels 310 of the piston.
- FIG. 1(G) Shown in FIG. 1(G) is a schematic drawing to illustrate another example of a compressing and consolidating operation (using a mold cavity cell equipped with a piston or ram) for forming a layer of highly compacted and oriented graphite flakes 320 .
- the piston is driven downward along the Y-direction.
- the graphite flakes are aligned on the X-Z plane and perpendicular to X-Y plane (along the Z- or thickness direction).
- This layer of oriented graphite flakes can be attached to a current collector (e.g. graphene mat) that is basically represented by the X-Y plane.
- graphite flakes are aligned perpendicular to the current collector.
- Such an orientation is conducive to a faster ion intercalation into and out of the spaces between graphite flakes and, hence, leads to a higher power density as compared to the corresponding electrode featuring graphite flakes being aligned parallel to the current collector plane.
- a multivalent metal-ion battery includes a positive electrode (cathode), a negative electrode (anode), and an electrolyte typically including a metal salt and a solvent.
- the anode can be a thin foil or film of a multivalent metal or its alloy with another element(s); e.g. 0-10% by weight of Sn in Zn.
- the multivalent metal may be selected from Ni, Zn, Be, Mg, Ca, Ba, La, Ti, Ta, Zr, Nb, Mn, V, Co, Fe, Cd, Cr, Ga, In, or a combination thereof.
- the anode can be composed of particles, fibers, wires, tubes, or discs of the multivalent metal or metal alloy that are packed and bonded together by a binder (preferably a conductive binder) to form an anode layer.
- a select multivalent metal e.g. Ni, Zn, Be, Mg, Ca, Ba, La, Ti, Ta, Zr, Mn, V, Co, Fe, Cd, Ga, or Cr
- a discharge curve plateau or average output voltage at approximately 1.0 volt or higher (up to 3.5 volts).
- This plateau regime of a discharge voltage vs. time (or capacity) curve enables the battery cell to provide a useful constant voltage output.
- a voltage output lower than 1 volt is generally considered as undesirable.
- the specific capacity corresponding to this plateau regime is typically from approximately 100 mAh/g (e.g. for Zr or Ta) to above 600 mAh/g (e.g. for Zn or Mg).
- a desirable anode layer structure is composed of a network of electron-conducting pathways (e.g. mat of graphene sheets, carbon nano-fibers, or carbon-nanotubes) and a thin layer of the multivalent metal or alloy coating deposited on surfaces of this conductive network structure.
- Such an integrated nano-structure may be composed of electrically conductive nanometer-scaled filaments that are interconnected to form a porous network of electron-conducting paths comprising interconnected pores, wherein the filaments have a transverse dimension less than 500 nm.
- Such filaments may comprise an electrically conductive material selected from the group consisting of electro-spun nano fibers, vapor-grown carbon or graphite nano fibers, carbon or graphite whiskers, carbon nano-tubes, nano-scaled graphene platelets, metal nano wires, and combinations thereof.
- an electrically conductive material selected from the group consisting of electro-spun nano fibers, vapor-grown carbon or graphite nano fibers, carbon or graphite whiskers, carbon nano-tubes, nano-scaled graphene platelets, metal nano wires, and combinations thereof.
- FIG. 2(A) Illustrated in FIG. 2(A) is a schematic of a multivalent metal secondary battery, wherein the anode layer is a thin multivalent metal coating or foil and the cathode active material layer contains a layer of thermally exfoliated graphite/carbon material that has been recompressed.
- FIG. 2(B) shows a schematic of a multivalent metal secondary battery cell wherein the cathode active material layer contains a layer of thermally exfoliated graphite/carbon material that has been recompressed, an optional conductive additive (not shown), and a resin binder (not shown) that helps to bond the worms together to form a cathode active layer of structural integrity.
- the recompressed exfoliated graphite or carbon materials when implemented as a cathode active material, enable the multivalent metal-ion cell to exhibit a voltage plateau portion in a discharge voltage-time or voltage-capacity curve obtained at a constant current density.
- This plateau portion typically occurs at a relatively high voltage value intrinsic to a given multivalent metal, and typically lasts a long time, giving rise to a high specific capacity.
- this plateau portion is followed by a slopping curve portion, corresponding to a supercapacitor-type behavior.
- the supercapacitor-type behavior (EDLC or redox) is due to the high specific surface area of the exfoliated graphite/carbon worms used in the cathode layer.
- the plateau portion is increased and slopping curve portion decreased when the degree of re-compression of worms is increased.
- composition of the electrolyte which functions as an ion-transporting medium for charge-discharge reaction, has a great effect on battery performance. To put multivalent metal secondary batteries to practical use, it is necessary to allow metal deposition-dissolution reaction to proceed smoothly and sufficiently even at relatively low temperature (e.g., room temperature).
- the electrolyte typically contains a metal salt dissolved in a liquid solvent.
- the solvent can be water, organic liquid, ionic liquid, organic-ionic liquid mixture, etc.
- the metal salt may be selected from NiSO 4 , ZnSO 4 , MgSO 4 , CaSO 4 , BaSO 4 , FeSO 4 , MnSO 4 , CoSO 4 , VSO 4 , TaSO 4 , CrSO 4 , CdSO 4 , GaSO 4 , Zr(SO 4 ) 2 , Nb 2 (SO 4 ) 3 , La 2 (SO 4 ) 3 , MgCl 2 , AlCl 3 , Mg(ClO 4 ) 2 , Mg(BF 4 ) 2 , Grignard reagents, magnesium dibutyldiphenyl, Mg(BPh2Bu2)2, magnesium tributylphenyl Mg(BPhBu3)2), or a combination thereof.
- the electrolyte may in general comprise at least a metal ion salt selected from a transition metal sulphate, transition metal phosphate, transition metal nitrate, transition metal acetate, transition metal carboxylate, transition metal chloride, transition metal bromide, transition metal nitride, transition metal perchlorate, transition metal hexafluorophosphate, transition metal borofluoride, transition metal hexafluoroarsenide, or a combination thereof.
- a metal ion salt selected from a transition metal sulphate, transition metal phosphate, transition metal nitrate, transition metal acetate, transition metal carboxylate, transition metal chloride, transition metal bromide, transition metal nitride, transition metal perchlorate, transition metal hexafluorophosphate, transition metal borofluoride, transition metal hexafluoroarsenide, or a combination thereof.
- the electrolyte comprises at least a metal ion salt selected from a metal sulphate, phosphate, nitrate, acetate, carboxylate, chloride, bromide, nitride, or perchlorate of zinc, aluminum, titanium, magnesium, calcium, manganese, cobalt, nickel, iron, vanadium, tantalum, gallium, chromium, cadmium, niobium, zirconium, lanthanum, or a combination thereof.
- a metal ion salt selected from a metal sulphate, phosphate, nitrate, acetate, carboxylate, chloride, bromide, nitride, or perchlorate of zinc, aluminum, titanium, magnesium, calcium, manganese, cobalt, nickel, iron, vanadium, tantalum, gallium, chromium, cadmium, niobium, zirconium, lanthanum, or a combination thereof.
- the electrolyte comprises an organic solvent selected from ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), methyl butyrate (MB), ethyl propionate, methyl propionate, propylene carbonate (PC), ⁇ -butyrolactone ( ⁇ -BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), tetrahydrofuran (THF), toluene, xylene, methyl acetate (MA), or a combination thereof.
- organic solvent selected from ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), methyl butyrate (MB), ethyl propionate, methyl propionate, propylene carbonate (PC), ⁇ -butyrolactone ( ⁇ -BL),
- This invention is directed at the cathode active layer (positive electrode layer) containing a high-capacity cathode material for the multivalent metal secondary battery.
- the invention also provides such a battery based on an aqueous electrolyte, a non-aqueous electrolyte, a molten salt electrolyte, a polymer gel electrolyte (e.g. containing a metal salt, a liquid, and a polymer dissolved in the liquid), an ionic liquid electrolyte, or a combination thereof.
- the shape of a multivalent metal secondary battery can be cylindrical, square, button-like, etc.
- the present invention is not limited to any battery shape or configuration.
- Natural flake graphite nominally sized at 45 ⁇ m, provided by Asbury Carbons (405 Old Main St., Asbury, N.J. 08802, USA) was milled to reduce the size to approximately 14 ⁇ m (Sample 1a).
- the chemicals used in the present study including fuming nitric acid (>90% concentration), sulfuric acid (95-98%), potassium chlorate (98%), and hydrochloric acid (37%), were purchased from Sigma-Aldrich and used as received.
- Graphite oxide (GO) samples were prepared according to the following procedure:
- Sample 1A A reaction flask containing a magnetic stir bar was charged with sulfuric acid (176 mL) and nitric acid (90 mL) and cooled by immersion in an ice bath. The acid mixture was stirred and allowed to cool for 15 min, and graphite (10 g) was added under vigorous stirring to avoid agglomeration. After the graphite powder was well dispersed, potassium chlorate (110 g) was added slowly over 15 min to avoid sudden increases in temperature. The reaction flask was loosely capped to allow evolution of gas from the reaction mixture, which was stirred for 24 hours at room temperature. On completion of the reaction, the mixture was poured into 8 L of deionized water and filtered.
- the GO was re-dispersed and washed in a 5% solution of HCl to remove sulphate ions.
- the filtrate was tested intermittently with barium chloride to determine if sulphate ions are present.
- the HCl washing step was repeated until this test was negative.
- the GO was then washed repeatedly with deionized water until the pH of the filtrate was neutral.
- the GO slurry was spray-dried and stored in a vacuum oven at 60° C. until it was used.
- Sample 1B The same procedure as in Sample 1A was followed, but the reaction time was 48 hours.
- Sample 1C The same procedure as in Sample 1A was followed, but the reaction time was 96 hours.
- Samples 1A, 1B, and 1C were then subjected to unconstrained thermal exfoliation (1,050° C. for 2 minutes) to obtain thermally exfoliated graphite worms.
- the graphite worms were compressed into layers of oriented, recompressed exfoliated graphite having physical density ranging from approximately 0.5 to 1.75 g/cm 3 , using both dry compression and wet compression procedures.
- Example 2 Oxidation and Intercalation of Various Graphitic Carbon and Graphite Materials
- Samples 2A, 2B, 2C, and 2D were prepared according to the same procedure used for Sample 1B, but the starting graphite materials were pieces of highly oriented pyrolytic graphite (HOPG), graphite fiber, graphitic carbon nano-fiber, and spheroidal graphite, respectively. Their final inter-planar spacing values are 6.6 ⁇ , 7.3 ⁇ , 7.3 ⁇ , and 6.6 ⁇ , respectively. Their un-treated counterparts are referred to as Sample 2a, 2b, 2c, and 2d, respectively. The treated samples were subsequently thermally exfoliated and recompressed to obtain samples of various controlled densities, specific surface areas, and degrees of orientation.
- HOPG highly oriented pyrolytic graphite
- Example 3 Preparation of Graphite Oxide Using a Modified Hummers' Method and Subsequent Thermal Exfoliation
- Graphite oxide (Sample 3A) was prepared by oxidation of natural graphite flakes (original size of 200 mesh, milled to approximately 15 ⁇ m, referred to as Sample 3a) with sulfuric acid, sodium nitrate, and potassium permanganate according to the method of Hummers [U.S. Pat. No. 2,798,878, Jul. 9, 1957].
- Sample 3a sulfuric acid, sodium nitrate, and potassium permanganate according to the method of Hummers [U.S. Pat. No. 2,798,878, Jul. 9, 1957].
- a mixture of 22 ml of concentrated sulfuric acid 2.8 grams of potassium permanganate, and 0.5 grams of sodium nitrate.
- the graphite flakes were immersed in the mixture solution and the reaction time was approximately one hour at 35° C.
- Some of the powder was subsequently exfoliated in a furnace, pre-set at 950-1,100° C., for 2 minutes to obtain thermally exfoliated graphite worms.
- the graphite worms were recompressed using both the wet and dry press-rolling procedures to obtain oriented, recompressed exfoliated graphite worms.
- Graphite oxide (Sample 4A) was prepared by oxidation of meso-carbon micro-beads (MCMBs) according to the same procedure used in Example 3.
- MCMB microbeads (Sample 4a) were supplied by China Steel Chemical Co. This material has a density of about 2.24 g/cm 3 , an average particle size of 16 ⁇ m, and an inter-planar distance of about 0.336 nm. After deep oxidation treatment, the inter-planar spacing in the resulting graphite oxide micro-beads is approximately 0.76 nm. The treated MCMBs were then thermally exfoliated at 900° C.
- exfoliated carbon which also showed a worm-like appearance (herein referred to as “exfoliated carbon”, “carbon worms,” or “exfoliated carbon worms”).
- the carbon worms were then roll-pressed to different extents to obtain recompressed exfoliated carbon having different densities, specific surface areas, and degrees of orientation.
- Graphitized carbon fiber (Sample 5a), having an inter-planar spacing of 3.37 ⁇ (0.337 nm) and a fiber diameter of 10 ⁇ m was first halogenated with a combination of bromine and iodine at temperatures ranging from 75° C. to 115° C. to form a bromine-iodine intercalation compound of graphite as an intermediate product. The intermediate product was then reacted with fluorine gas at temperatures ranging from 275° C. to 450° C. to form the CF y . The value of y in the CF y samples was approximately 0.6-0.9.
- X-ray diffraction curves typically show the co-existence of two peaks corresponding to 0.59 nm and 0.88 nm, respectively.
- Sample 5A exhibits substantially 0.59 nm peak only and Sample 5B exhibits substantially 0.88 nm peak only.
- Fluorine gas was introduced into a reactor and the reaction was allowed to proceed at 375° C. for 120 hours while maintaining the fluorine pressure at 200 mmHg. This was based on the procedure suggested by Watanabe, et al. disclosed in U.S. Pat. No. 4,139,474.
- the powder product obtained was black in color.
- the fluorine content of the product was measured as follows: The product was burnt according to the oxygen flask combustion method and the fluorine was absorbed into water as hydrogen fluoride.
- Sample 7B was obtained in a manner similar to that for Sample 7A, but at a reaction temperature of 640° C. for 5 hours.
- the chemical composition was determined to be (CF 0.93 ) n .
- Some of the graphite fluoride powder was thermally exfoliated to form graphite worms, which were then roll-pressed to produce recompressed exfoliated graphite material.
- the exfoliated carbon/graphite materials prepared in Examples 1-7 were separately made into a cathode layer and incorporated into a multivalent metal secondary battery.
- Two types of multivalent metal anode were prepared. One was metal foil having a thickness from 20 ⁇ m to 300 ⁇ m. The other was metal thin coating deposited on surfaces of conductive nano-filaments (e.g. CNTs) or graphene sheets that form an integrated 3D network of electron-conducting pathways having pores and pore walls to accept a multivalent metal or its alloy. Either the metal foil itself or the integrated 3D nano-structure also serves as the anode current collector.
- conductive nano-filaments e.g. CNTs
- graphene sheets that form an integrated 3D network of electron-conducting pathways having pores and pore walls to accept a multivalent metal or its alloy. Either the metal foil itself or the integrated 3D nano-structure also serves as the anode current collector.
- Cyclic voltammetry (CV) measurements were carried out using an Arbin electrochemical workstation at a typical scanning rate of 0.5-50 mV/s.
- the electrochemical performances of various cells were also evaluated by galvanostatic charge/discharge cycling at a current density from 50 mA/g to 10 A/g.
- galvanostatic charge/discharge cycling at a current density from 50 mA/g to 10 A/g.
- multi-channel battery testers manufactured by LAND were used for long-term cycling tests.
- FIG. 3(A) shows the discharge curves of three Zn foil anode-based Zn-ion cells: first one containing a cathode layer of original graphite particles, second one containing a cathode layer of thermally exfoliated graphite (with only light recompression; pore size from 20 nm to 3 ⁇ m), and third one containing a cathode layer of thermally exfoliated graphite (with heavy recompression; pore size range from approximately 2 nm to 20 nm; having an edge plane being parallel to the separator and in contact with the separator).
- the electrolyte used was 1M of ZnSO 4 in water.
- FIG. 3(B) shows discharge curves of two Ca-ion cells: one containing a cathode layer of thermally exfoliated graphite (with heavy recompression) having a flake edge plane being parallel to the separator and in ionic contact with the separator); the other having a graphite flake surface plane being parallel to the separator and in contact with the separator.
- the cell containing a cathode of original artificial graphite particles exhibits a very short discharge curve ( ⁇ 30 mAh/g); not shown in the chart.
- cathode layer of oriented recompressed graphite worms exhibits an initial plateau regime corresponding to ion intercalation into the graphitic structure and a slopping curve portion corresponding to adsorption of Ca ions or other electrolyte-derived ions on graphite flake surfaces.
- the cell has a significantly higher specific capacity (250 mAh/g) as compared to the cathode featuring unfavorably oriented compressed worms (70 mAh/g). The latter is only capable of storing Ca ions via the surface adsorption or electroplating mechanism.
- Shown in FIG. 4 are the discharge curves of two Ni mesh anode-based Ni-ion cells, one containing a cathode layer of original MCMB particles and the other a cathode layer of recompressed exfoliated MCMBs.
- the recompressed MCMB worms enable the MCMB to admit (via intercalation and then surface adsorption) and store a large amount of ions (up to 450 mAh/g).
- the original MCMB beads with unexpanded inter-planar spacing stores a very limited amount of Ni ions, mostly due to electroplating at very low voltage levels. There is typically very short or no plateau regime in a charge or discharge curve for a multivalent metal-graphite/carbon cell having untreated, original carbon/graphite as the cathode active material.
- the present invention provides a powerful platform materials engineering technology for enhancing the specific capacity of carbon or graphite cathode materials implemented in a multivalent metal-ion battery.
- both the Zn-MCMB cell (containing a cathode layer of recompressed, exfoliated MCMB) and the Vanadium-CNF cell (containing a cathode of vapor grown carbon nanofibers that have been exfoliated and recompressed) show exceptionally stable cycle life, exhibiting less than 20% capacity degradation after 5,000 charge-discharge cycles.
- the cycle life of the presently invented multivalent metal-ion cell is typically significantly higher than the cycle life of the lithium-ion battery.
- FIG. 6 shows that the specific capacity of a Mg-ion cell containing a cathode layer of favorably oriented, heavily recompressed exfoliated MCMBs is significantly higher than the specific capacity of a Mg-ion cell containing a cathode of lightly recompressed exfoliated MCMBs.
- the edge plane orientation relative to the separator plane plays a critical role in dictating the charge storage capability.
- a Mg-ion cell having a CNT-supported Mg anode and a cathode layer containing recompressed exfoliated artificial graphite a Mg-ion cell having a Mg foil anode (no CNT support) and a cathode layer containing recompressed exfoliated artificial graphite
- a Ca-ion cell having a graphene-supported Ca anode and a cathode layer containing recompressed exfoliated artificial graphite a Ca-ion cell having a Ca anode (no graphene support) and a cathode layer containing recompressed exfoliated artificial graphite.
- Both Mg-ion cells and Ca-ion cells deliver energy densities comparable to those of lithium-ion batteries, but higher power densities.
- the power density values are comparable to those of supercapacitors.
- the presently invented multivalent metal-ion batteries have the best of both worlds of lithium-ion batteries and supercapacitors.
- This nano-structured network of interconnected carbon nano-fibers provides large surface areas to support multivalent metal and facilitate fast and uniform dissolution and deposition of metal cations at the anode side.
- This strategy also has overcome the passivating layer issue commonly associated with Mg or Ca metal anode.
- Other nano-filaments or nano-structures that can be used to make such a network include electro-spun nano fibers, vapor-grown carbon or graphite nano fibers, carbon or graphite whiskers, carbon nano-tubes, nano-scaled graphene platelets, metal nano wires, or a combination thereof.
Abstract
Description
- (1) There is no plateau portion in the charge or discharge curves (voltage vs. time or voltage vs. specific capacity), unlike typical lithium-ion batteries. This lack of a voltage curve plateau means the output voltage being non-constant (varying too much) and would require a complicated voltage regulation algorithm to maintain the cell output voltage at a constant level.
- (2) Actually, the discharge curve for the Ni-ion cell exhibits an extremely sharp drop in voltage from 1.5 volts to below 0.6 volts as soon as the discharge process begins and, during most of the discharge process, the cell output is below 0.6 volts, which is not very useful. As a point of reference, the alkaline cell (a primary battery) provides an output voltage of 1.5 volts.
- (3) The discharge curves are characteristic of surface adsorption or electroplating mechanisms at the cathode, as opposed to ion intercalation. Further, it appears that the main event that occurs at the cathode during the battery discharge is electroplating. The high specific capacity values reported by Xu, et al. are simply a reflection on the high amount of Ni or Zn metal electroplated on the surfaces of graphene or CNTs. Since there is an excess amount of Ni or Zn in the anode, the amount of electroplated metal increases as the discharge time increases. Unfortunately, the electrochemical potential difference between the anode and the cathode continues to decrease since the difference in the metal amount between the anode and the cathode continues to decrease (more Zn or Ni is dissolved from the anode and gets electroplated on cathode surfaces). This is likely why the cell output voltage continues to decrease. The cell voltage output would be essentially zero when the amounts of metal at the two electrodes are substantially equivalent or identical. Another implication of this electroplating mechanism is the notion that the total amount of the metal that can be deposited on the massive surfaces at the cathode is dictated by the amount of the metal implemented at the anode when the cell is made. The high specific capacity (as high as 2,500 mAh/g) of graphene sheets at the cathode simply reflects the excessively high amount of Zn provided in the anode. There is no other reason or mechanism for why graphene or CNTs could “store” so much metal. The abnormally high specific capacity values as reported by Xu, et al. were artificially obtained based on the high amounts of Ni or Zn electroplated on cathode material surfaces, which unfortunately occurred at very low voltage values and are of little utility value.
TABLE 1 |
Plateau voltage ranges of the discharge |
curves in multivalent metal-ion cells. |
Anode Metal | Voltage range | ||
Ba | 3.40-3.55 V | ||
Ca | 3.25-3.35 V | ||
La | 2.91-3.05 V | ||
Mg | 2.85-3.01 V | ||
Be | 2.40-2.51 V | ||
Ti | 2.18-2.22 V | ||
Zr | 1.98-2.07 V | ||
Mn | 1.78-1.85 V | ||
V | 1.75-1.82 V | ||
Nb | 1.67-1.73 V | ||
Zn | 1.20-1.35 V | ||
Cr | 1.16-1.31 V | ||
Ta | 1.17-1.25 V | ||
Ga | 1.09-1.18 V | ||
Fe | 0.96-1.13 V | ||
Cd | 0.95-1.10 V | ||
Co | 0.87-0.98 V | ||
Ni | 0.85-0.95 V | ||
TABLE 2 |
A list of carbon or graphite materials used as the cathode active material of an Al cell. |
Specific | Specific | Specific | |||
Sample | Inter-planar | capacity, | capacity, | capacity, | |
No. | Material | spacing, Å | mAh/g (Zn) | mAh/g (V) | mAh/g (Mg) |
1a | Natural graphite | 3.35 | 22 | 25 | |
1A | GO, 24 hrs | 5.5 | 223 | 211 | |
1B | GO, 48 |
7 | 301 | 287 | |
1C | GO, 96 hrs | 7.6 | 346 | 269 | |
2a | HOPG | 3.35 | 21 | 27 | |
2A | HOPG oxide | 6.6 | 287 | 204 | |
2b | Graphite fiber | 3.4 | 16 | 32 | |
2B | Oxidized GF | 7.3 | 323 | 205 | |
2c | CNF | 3.36 | 45 | 77 | |
2C | Oxidized CNF | 7.3 | 332 | 277 | |
3a | Natural graphite | 3.35 | 17 | ||
3A | GO, Hummers | 7.3 | 214 | ||
4a | MCMB | 3.36 | 22 | ||
4A | Oxidized MCMB | 7.6 | 261 | ||
5a | Graphite fiber | 3.4 | 16 | ||
5A | CF0.9 | 8.8 | 343 | ||
5B | CF0.6 | 5.9 | 204 | ||
6A | CBrFx | 8.4 | 325 | ||
7A | CF0.75 | 5.85 | 202 | ||
7B | CF0.93 | 9.2 | 406 | ||
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JP7340454B2 (en) | 2023-09-07 |
US20200251735A1 (en) | 2020-08-06 |
CN110520952A (en) | 2019-11-29 |
WO2018175086A1 (en) | 2018-09-27 |
JP2020510301A (en) | 2020-04-02 |
US11515536B2 (en) | 2022-11-29 |
US20180269479A1 (en) | 2018-09-20 |
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